Hydrogenated olefin sulfonate-fatty acid amide detergent compositions

ABSTRACT

High performance detergent compositions comprise a mixture of hydrogenated olefin sulfonates and a selected amide or substituted amide.

United States Patent Shannan [451 July 1 1, 1972 s41 HYDROGENATED OLEFIN[56] References Cited glkgONATE-FATIY ACID AMIDE UNITED STATES PATENTSRGENT C0 SITIONS 3,332,878 7/ 1967 Coward et al ....252/ l 52 [72]Inventor: Samuel H. Shannan, Berkeley, Calif. 3,345,301 10/ I967 Steinet al ..252/ l 52 Assignee: Chevron p y San Fran BEN-158811811 l 3cisco, n 3,428,654 2/ 1969 Rubmfeld et a1. ..260/ 327 3,444,087 5/1969Eccles et al ..252/138 [22] Flledz Oct. 24, 1968 [2]] Appl. No.: 770,415Primary Examiner-Leon D. Rosdol Assistant ExaminerP. E. Willis [52] U SCl 252/525 252/535 252/536 AtI0mey--A. L. Snow, F. E. Johnston and JohnStoner, Jr.

252/544, 252/554, 252/555 511 men ..Clld3/066,Clld 1/12 [571 ABSTRACT[58] held of Search ..252/l 37, 138, 161, 125626255? High performancedetergent compositions comprise a mixture of hydrogenated olefinsulfonates and a selected amide or substituted amide.

7 Claims, No Drawings HYDROGENATED OLEFIN SULFONATE-FATIY ACID AMIDEDETERGENT COMPOSITIONS BACKGROUND OF INVENTION Recent concern over waterpollution has resultedfin significant changes in the active ingredientof modern detergents. Extensive and expensive research has been directedat discovering suitable detergent compounds which are both readilybiodegradable and possess highdetersive properties.

Heretofore, however, known commercial detergent compounds whichpossessed high detersive properties were not as- DESCRIPTION OFINVENTION It has now been found that superior detergent compositionscomprise a mixture of straight-chain hydrogenatedolefin sulfonatescontaining from 10 to 24 carbon atoms, and selected substituted andunsubstituted amides. In particular, the performance of the describedmixture is significantly greater than would be predicted from aknowledge of the performance of the individual components as well asother compounds.

The term hydrogenated. olefin sulfonates as used in the presentinvention defines the complex mixture obtained by the S sulfonation ofstraight-chain olefins containing to 24 carbon'atoms and subsequentneutralization, hydrolysis and hydrogenation of the sulfonation reactionproduct. This complex mixture may contain hydroxyalkane, alkane andalkene sulfonates as its major components and a lesser proportion ofdisulfonated product.

While the general nature of the major components of the complex mixtureis known, the specific identity and the relative proportions of thevarious hydroxy, sulfonate and disulfonate radicals and double bondlocations are unknown. Accordingly, a determination of the entirechemical makeup is exceedingly difficult and has not heretofore beensuccessfully accomplished. The mixture is best defined by the processused for producing it.

Optimum detergent characteristics are exhibited by a hydrogenated olefinsulfonate obtained by SO -air sulfonation of C F24 straight-chainolefins with an SO;,:air volume ratio of about 1 to 50-100 and SO:olefin mol ratio of 0.95 to 1.15; neutralization and hydrolysis of thesulfonation reaction product at temperatures of 145 to 200 C. using oneequivalent of base per mol of S0 consumed in the sulfonation step;treatment of the sulfonate product with air, oxygen, or hydrogenperoxide; and hydrogenation in the presence of Raney nickel or palladiumon carbon catalysts at temperatures of from 70 to 120 C.

In addition to the preferred straightchain alpha-olefins from waxcracking suitable olefin starting materials include straight-chainalpha-olefins produced by Ziegler polymerization of ethylene, orinternal straight-chain olefins prepared by catalytic dehydrogenation ofnormal paraffins or by chlorination-dehydrochlorination of normalparaffins. The olefins may containfrom 10 to 24 carbon atoms, usually 13to 22 carbon atoms, and preferably 15 to 18 carbon atoms per molecule.Olefin mixtures should have an average molecular weight of at leastabout 200.

The amount of SO utilized in the sulfonation reaction may be varied butis usually within the range of 0.95 to 1.25 mols of SO per mol ofolefinand preferably in in the range 1:1 to 1:1.15. Greater formation ofdisulfonated products is observed at higher sO zolefin ratios.Disulfonation may be reduced by carrying the sulfonation reaction onlyto partial conversion of the olefin, for example by using so zolefinratios of less than 1 and removing the unreacted olefins by a deoilingprocess. The unreacted olefins may be removed by extracting the reactionproduct with a hydrocarbon such as pentane.

In order to obtain a product of good color, the employed in thesulfonation reaction is generally mixed with an inert diluent or with amodifying agent. Inert diluents which are satisfactory for this purposeinclude air, nitrogen, 50;, dichloromethane, etc. The volume ratio of $0to diluent is usually within the range of 1:100 to l l.

The reaction product from the sulfonation step may be neutralized withaqueous basic solutions containing compounds such as hydroxides,carbonates and oxides of the alkali metals, alkaline earth metals andammonium. 1n the preferred method, sufficient neutralizing solution maybe added to provide for neutralization of the hydroxyalkane sulfonicacids formed by sultone hydrolysis. Generally, one equivalent of basefor each mole of S0 consumed in the sulfonation reaction is added to thesulfonation reaction product.

The proportion of hydroxyalkane sulfonates to alkene sulfonates in thehydrolyzed neutralized product may be varied somewhat by the manner inwhich neutralization and hydrolysis are carried out. Thus, reducedamounts of hydroxyalkane sulfonates are obtained by carrying out theneutralization and hydrolysis at temperatures in the range of l45-200 C.while higher yields of hydroxy sulfonate are favored by carrying out theneutralization and hydrolysis at temperatures below C. Suitablehydrolysis temperatures range from about 100 to 200 C.

Amides suitable for producing the excellent detergent compositions ofthe present invention may be represented by the formula 0 Il -C NHR:

wherein R is a straight-chain alkyl radical containing from 10 to 17carbon atoms and R is hydrogen or an alkyl radical containing from 1 tothree carbon atomsv The amide component of the detergent compositionneed not be limited to compounds containing alkyl radicals of a singleset carbon number, but may include mixtures thereof, such as found incoconut amide.

In addition, when substituted amides are utilized. they likewise neednot be of the same type of substitution. For example, a mixture ofSOpercent coconut amide and SOpercent of N-methylhexadecanarnide iswithin the scope of the present invention.

Specific examples of amides suitable for use in the present invention,but by no means an exhaustive list include: dodecanamide, tridecanamide,tetradecanamide, pen tadecanamide, hexadecanamide, heptadecanamide,octadecanamide, N-methyldo-decanamide, N-methyltridecanamide,N-methyltetradecanamide, N-methylpentadecanamide,N-methylhexadecanamide, N-methylhepta'decanamide andN-methyloctadecanamide, etc.

The selected amides or mixtures thereof may comprise from 5 to 35 partsper hundred parts by weight of hydrogenated olefin sulfonate of thedetergent composition. The most desirable ratio is usually from 10 to 20parts per hundred parts by weight of olefin sulfonate.

The following examples describe the preparation of hydrogenated olefinsulfonates, their precursor olefin sulfonates and the novel detergentcompositions of the present invention.

EXAMPLE 1 Preparation of Olefin Sulfonates The reactor used for thissulfonation consisted of a continuous falling film-type unit in the formof a vertical waterjacketed tube. Both the olefin and the S air mixturewere introduced at the top of the reactor and flowed concurrently downto the reactor. At the bottom the sulfonated product was separated fromthe air stream.

The feed was a straight-chain l-olefin blend produced by cracking highlyparaffinic wax and having the following composition by weight: lpercenttetradecene, 27percent pentadecene, 29percent hexadecene, 28percentheptadecene, l4percent octadecene and lpercent nonodecene. This materialwas charged to the top of the above described reactor at a rate of 206pounds/hour. At the same time 124.2 pounds/hour of SO diluted with airto 3percent by volume concentration of 80;, was introduced into the topof the reactor. The reactor was cooled with water to maintain thetemperature of the effluent product within the range of 4346 C. Theaverage residenee time of the reactants in the reactor was less than 2minutes.

After passing out of the reactor the sulfonated product was mixed with612 pounds/hour of 11.2percent aqueous caustic and heated to l45l50 C.in a tubular reactor at an average residence time of 30 minutes. Thisstep neutralized the sulfonic acids contained in the sulfonationreaction product, hydrolyzed the sultones to hydroxy sulfonic acids andneutral ized the hydroxy sulfonic acids. Olefin sulfonates were producedat the rate of 463 pounds per hour as an aqueous solution having a45percent by weight solids content and a pH of 10.8.

A portion of this product was analyzed and shown to be made up of thesodium salts of alkene sulfonic acids, hydroxy alkane sulfonic acids,and disulfonic acids. These three major components were present in aweight ratio of about 50/35/15.

EXAMPLE 2 Preparation of C1540 Olefin Sulfonates A straight-chainl-olefin mixture produced by cracking a highly paraffinic wax andcontaining lpercent tetradecene, l8percent pentadecene, l7percenthexadecene, l6percent heptadecene, l6percent octadecene, l4percentnonadecene, l3percent eicosene and percent heneicosene was processedfollowing the procedure in Example 1.

EXAMPLE 3 Preparation of Hydrogenated Olefin sulfonates The apparatusfor this hydrogenation consisted of a l-liter Magne-Drive autoclaveequipped with an accumulator, a constant pressure regulator, and atemperature recording means. The product of Example 1 was diluted withwater to a 26percent solids concentration and was filtered to remove atrace amount of insoluble material. The pH was adjusted to a value of6.5-7.5 by neutralizing the slight excess of NaOH used in theneutralization and hydrolysis step with H SO and 100 parts of 30percenthydrogen peroxide was added to 3,850 parts of the filtered 26percentsolution in an open glass vessel. This mixture was heated to 80 C. andstirred for 1 hour at this temperature, after which time no hydrogenperoxide remained. After cooling this solution to room temperature, 650g. of it was charged to the previously described autoclave along with8.5 g. of Raney nickel. The system was purged with nitrogen and thenwith hydrogen. It was then pressured with hydrogen to 50 psig. Theautoclave was warmed to 100 C. at which temperature hydrogen was againintroduced to bring the pressure up to 100 psig. The hydrogen pressurewas maintained constant at 100 psig. throughout the run. After 1% hoursof stirring at this temperature and pressure, and at which time therewas no additional hydrogen uptake, the solution was cooled to about 70C., filtered and then allowed to cool.

EXAMPLE 4 Preparation of Hydrogenated Olefin Sulfonates The product ofExample 2 was reduced as in Example 3 to give a substantially l00percentreduction of double bonds in the olefin sulfonate.

The hydrogen peroxide treating step prior to hydrogenation increaseshydrogenation efficiency. The olefin sulfonate prior to such treatmentcontains unidentified compounds which poison hydrogenation catalysts.Without the hydrogen peroxide pretreat catalyst consumption is muchhigher. Other oxidizing agents may be used instead of hydrogen peroxidein the pretreating step, preferably oxidizing agents which leave nosolid residues in the product such as elemental oxygen or air.

in addition to the Raney nickel exemplified, a wide variety of knownhydrogenation catalysts may be used in the hydrogenation step. Theseinclude the noble metals and various forms of nickel other than Raneynickel such as nickel on kieselguhr, and other supported nickelcatalysts. Palladium on carbon and ruthenium on alumina are effectivenoble metal catalysts, although Raney nickel and palladium on carbon arepreferred catalysts.

The amount of catalyst employed in the hydrogenation of olefinsulfonates may vary in a range from about 0.05 to 30percent by weightbased on the olefin sulfonate present. Increasing the amount of catalystwill usually result in a shortening of the time necessary for completehydrogenation.

The hydrogenation reaction is usually carried out at temperatures fromabout 20 C. to about 200 C. and preferably 70 C. to C. At temperaturesappreciably above 200 C. unnecessary hydrogenation of hydroxyalkanesulfonates and hydrogenative degradation of the product tend to occur.

Hydrogen pressure during the reaction is not a critical variable.Reduction may be carried out at pressures varying from less thanatmospheric to 5,000 psig, but preferably from 30 to 200 psig.

In Examples 3 and 4 above hydrogenation of the alkene sulfonatecomponent of the neutralized sulfonation reaction mixture to alkanesulfonate was essentially complete. Partial hydrogenation of the olefinsulfonate to the extent that at least SOpercent of the alkene sulfonateis converted to alkane sulfonate yields a hydrogenated olefin sulfonatesuitable for use in producing high quality non-soap detergent bars.Partial hydrogenation may be accomplished by proceeding as in Example 3but discontinuing the hydrogenation reaction before hydrogen take-upceases. Partial hydrogenation can also be carried out by subjecting theolefin sulfonate to hydrogenation after neutralization but prior tohydrolysis.

EXAMPLE 5 Preparation of Partially Hydrogenated Olefin Sulfonate Theprocedure of Example 3 was followed except that reduction was allowed tocontinue for only 30 minutes. The product was worked up as before.Analysis of a small aliquot by bromine number titration showed that55percent of the double bonds originally contained had been saturated.

EXAMPLE 6 Hydrogenation of an Unhydrolyzed Olefin Sulfonate l-Hexadecenewas sulfonated in a continuous falling-film reactor with SO /olefin mo]ratio of about 1.2. The product from this reaction, 184 g. was dissolvedin 198 g. of dioxane to give a 48percent solution.

Fifty g. of this 48percent solution was heated with stirring to 60 C.Then 2.1 g. of 34percent hydrogen peroxide was added. Stirring wascontinued at this temperature for 1 hour. The solution was allowed tocool to room temperature.

Of the hydrogen peroxide treated material, 17.3 g. was diluted to 50 ml.with dioxane and charged to a 200 ml.

F ischer-Porter bottle along with 0.80 g. of Spercent palladium oncarbon hydrogenation catalyst. The mixture was heated to 24-26 C. andpressured to 50.5 psig with hydrogen. After 30 minutes of reaction, thepressure had dropped 18.4 psig. No further drop in pressure occurredafter this time. This pressure drop corresponds to hydrogenation of 3lpercent of the original olefin-S reaction product.

The hydrogenated material was filtered to remove the catalyst. Thedioxane was removed by evaporation at temperatures below 40 C. underreduced pressure. In this way, there was obtained 8.3 g. of a lowmelting solid. A portion of this solid, 6.4 g. was mixed with 2.0 g. of50percent aqueous sodium hydroxide in 35 ml. of water and heated at150155 C. for 2 hours. The water was then removed by evaporation. Abromine number analysis of the final product indicated that about25percent of the product was unsaturated. Accordingly, the calculatedweight ratio of hydroxyalkane, alkene and a1- kane sulfonates would be44/25/31, respectively.

EXAMPLE 7 Preparation of Detergent Composition A sample of hydrogenatedolefin sulfonates produced in accordance with Example 4 was formulatedwith an amide and other ingredients into a household detergentcomposition. The percentages of the various ingredients based on thetotal weight of the formulation were:

Hydrogenated olefin sulfonate 21 Coconut amide 4 Sodium tripolyphosphate40 Carboxy methyl cellulose 1 Sodium silicate 7 Sodium sulfate 19 Water8 Total 100% Mixed amide having 8% C 7% C 49% C 17%C 9% C and 10% c Thedetergent formulation was dissolved in water to a 0.lpercent by weightconcentration and evaluated by use of the Hand Dishwashing Test". TheHand Dishwashing Test isan effective means for evaluating the detersivecharacteristics of detergent compositions and is based on a procedurepresented at the ASTM D-12 Subcommittee on Detergents, Mar. 10, 1949,New York, New York. The test measures under simulated home washingconditions the number of plates or dishes washed before foam collapses.

The composition of Example 7 gave an excellent rating of 30 plates bythis test. In comparison a sample of olefin sulfonates prepared inaccordance with Example 1 was formulated as above and tested, but gave arating of only 25 plates.

EXAMPLE 8 A sample of hydrogenated olefin sulfonates was prepared inaccordance with Example 4 and separated into two portions. The firstportion, 25 parts, was dissolved in 75 parts of water. This solution wasevaluated at 0.l5percent concentration in the dishwashing test and gavea low rating of only six plates. A similar solution of olefin sulfonatesprepared in accordance with Example 1 was dissolved in water for arating of 20 plates.

EXAMPLE 9 The second portion from Example 8 was combined with 19 partsof coconut amide per hundred parts of hydrogenated olefin sulfonate, and25 parts of this mixture was dissolved in 75 parts of water. Evaluationof this composition at 0.l5percent concentration gave a rating of 16plates, an improvement of over 250percent.

Detergent compositions were prepared in accordance with Example 7 exceptthat different amounts and amides were substituted for coconut amide.The results obtained in the dishwashing test are shown in Table l.

TABLE I I Ex. Amide Amount Plates 7 Coconut amide 20/105 30 10Docosanamlde 20/ 105 12 l 1 Dodecanarnlde 20/ 105 28 12 Coconut Amide30/95 30 13 Decanomlde 20/105 24 14 None 24 Parts of amide per/parts ofhydrogenated olefin sulfonate.

Another effective means for measuring the properties of 'detergentcompositions is known as the Bench Foam Test. In a representative testseries solutions of 0.0Spercent by weight concentration of formulationswere prepared in aliquots of 1,000 ml. The test consisted ofmechanically stirring the test solutions, after heating to 120 i 10 F ina 2,000 ml. beaker for 1 minute, and measuring the foam height in mm. at0, and after 10 minutes. Foam heights of ll and 8 mm. at 0 and 10minutes are considered satisfactory.

EXAMPLE 15 The Bench Foam Test correlates well with the dishwashingtest. For example, a test on a sample prepared in accordance withExample 8 gave foam heights of 9 and 7 mm. at 0 and 10 minutesrespectively. Foam heights of 14 and 13 mm. were observed for a sampleprepared in accordance with Example 9 in a ratio of 20 parts of coconutamide per parts of hydrogenated olefin sulfonate.

A sample prepared in accordance with Example lo in a ratio of 10 partsof docosanamide per parts of hydrogenated olefin sulfonate gave foamheights of 7 and 6 mm. respectively.

Similar tests were run on various amides and the results are given inTable II.

Made to 0.05% by weight concentration in water. Parts of amide/per partsof hydrogenated olefin sulfonate.

Additional compatible ingredients may be incorporated into the detergentcompositions prepared in accordance with the present invention toenhance their detergent properties. Particularly effective is theincorporation of certain pentavalent phosphoric acid salts. For example,suitable phosphates would include, but are not limited to: sodiumtripolyphosphate, potassium tripolyphosphate, ammonium tripolyphosphate,tetrasodium pyrophosphate, tetrapotassium pyrophosphate, trisodiumphosphate, tripotassium phosphate, ammonium phosphate, sodiumhexametaphosphate, potassium hexametaphosphate, ammoniumhexametaphosphate, monosodium orthophosphate, monopotassiumorthophosphate, disodiurn orthophosphate, dipotassium orthophosphate andthe like.

An effective amount of alkali pentavalent phosphoric acid salt usuallycomprises from about 0.2 to 3 parts per parts by weight of hydrogenatedolefin sulfonate. Preferably, the ratio is l to 2 parts per part byweight of hydrogenated olefin sulfonate.

Other compatible ingredients which may be incorporated C. of the sultonecontent of said mixture;and into the detergent compositions of thepresent invention in- 3. neutralization of said mixture; and cludeanticorrosion, antiredeposition, chemical bleaching and B. an amide, ofthe formula sequestering agents; optical whiteners and certain inorganicsalts other than phosphate, such as inorganic sulfates, car- 0 bonatesor borates. The appropriate quantities and compositions of theseadditives, agents and builders are well described Bro in the art. NHR;

Iclaim: 1. A detergent composition having improved detersive wherein R,is a straight-chain alkyl radical containing from characteristicsconsisting essentially of 10 to 17 carbon atoms and R is hydrogen or analkyl A. a mixture of hydrogenated olefin sulfonates obtained by radicalContaining from one to three Carbon atoms, in a sulfonatingstraight-chain olefins containing from 10 to io f 5 i0 35 parts perhundred parts by weight of 24 carbon atoms with S0 wherein the amount ofS0,, is y g n Olefin sulfonatewithin the range of 0.95 to 1.25 mols ofso per mol of A detergent Composition as in Claim 1 wherein the olefin,and wherein said sulfonated olefins are sub- Straight-chain Olefin-5 arealpha'olefinssequently subjected to, in any desired sequence, the stepsA detergent composition as in Claim 2 where!" the f; straight-chainolefins contain from 15 to carbon atoms.

1. treating with an oxidizing agent selected from the A detergentcomposition as in claim 3 wherein the amide group consisting of hydrogenperoxide, elemental 20 is present in an amount of from 10 to 20 partsper hundred ygen, and air in an amount sufficient to improve the PartsOfhydrogenated Olefin Q hydrogenatability th f and hydmgenating Said 5.A detergent composition as in claim 4 wherein from 75 to treatedsulfonated olefins with a conventional 100 Percent of carbon'cal'bondouble bonds are hydrogenation catalyst at a temperature of from abouthydrogenated- 20 to 200 C" said catalyst being employed in an 6. Adetergent composition as in claim 4 wherein R conamount of from about0.05 to percent by weight tams from 11 to 13 Carbon atoms nd R lShydrogen.

based upon the olefin sulfonate content, the 7. A detergent compositionof claim 1 which contains as an hydrogenation being allowed to proceeduntil f 50 additional adjuvant an alkali metal pentavalent phosphoric tolOO percent of the unsaturated carbon-carbon douacid salt In an amountof from to 3 Pans by of ble bonds therein are saturated; 30 hydrogenatedolefin sulfonate- 2. hydrolysis at a temperature of from about 100 to200

2. A detergent composition as in claim 1 wherein the straight-chainolefins are alpha-olefins.
 2. hydrolysis at a temperature of from about100* to 200* C. of the sultone content of said mixture; and 3.neutralization of said mixture; and B. an amide, of the formula whereinR1 is a straight-chain alkyl radical containing from 10 to 17 carbonatoms and R2 is hydrogen or an alkyl radical containing from one tothree carbon atoms, in a ratio of 5 to 35 parts per hundred parts byweight of hydrogenated olefin sulfonate.
 3. A detergent composition asin claim 2 wherein the straight-chain olefins contain from 15 to 20carbon atoms.
 4. A detergent composition as in claim 3 wherein the amideis present in an amount of from 10 to 20 parts per hundred parts ofhydrogenated olefin sulfonates.
 5. A detergent composition as in claim 4wherein from 75 to 100 percent of carbon-carbon double bonds arehydrogenated.
 6. A detergent composition as in claim 4 wherein R1contains from 11 to 13 carbon atoms and R2 is hydrogen.
 7. A detergentcomposition of claim 1 which contains as an additional adjuvant analkali metal pentavalent phosphoric acid salt in an amount of from 0.2to 3 parts by weight of hydrogenated olefin sulfonate.